Pillar[5]arene based conjugated macrocycle polymers with unique photocatalytic selectivity

The development of heterogeneous catalysts with substrate shape, size or electronic constitution selectivity is a huge challenge in photocatalysis. Reported herein is a host-guest interaction strategy to endow photocatalysts with special selectivity. By adjusting the precursors, conjugated macrocycle polymers (CMPs) with pillar[5]arene struts (CMP-1 and CMP-2) and a corresponding non-pillar[5]arene-contained conjugated organic polymer (COP-1) were prepared and the photocatalytic activities toward sulfide derivatives were investigated. The sulfides showed similar conversions when COP-1 was used as a photocatalyst, but exhibited significant differences when it turned to the CMPs. Remarkably, the conversion yield of S-1 achieved near 18 folds over the one of S-2 when CMP-2 was used as a catalyst. Mechanism studies confirmed that the “host-guest” effect of pillar[5]arene struts in CMPs was the main cause of the difference. The present work establishes CMPs as novel heterogeneous photocatalysts with substrate selectivity, and such a method will inspire the researchers concerning preparation of heterogeneous catalysts with excellent selectivity.     

Spatial variability and radiation assessment of the radionuclides in soils and sediments around a uranium tailings reservoir,south of China

Journal of Radioanalytical and Nuclear Chemistry - The concentrations of 238U, 226Ra, 232Th and 40K and gross α, β were measured in soils and sediments around a uranium tailings reservoir...     

多集值信息表中的多粒度模糊决策论粗糙集

多粒度粗糙集和决策论粗糙集是Pawlak粗糙集的重要推广,目前已成为人工智能研究的热点.然而,它们大多处理的都是单值信息系统中的问题.而实际生活中绝大多数都是处理多值问题,为了解决这一问题,在多集值信息表中将多粒粗糙集与模糊决策论粗糙集相结合进行研究,提出了其在乐观,悲观情形下的上下近似,研究了一些相关性质并给出了多集值信息表中的多粒度模糊决策论粗糙集精度、粗度的概念,最后通过一个具体例子验证其有效性.     

多孔活性自燃金属的光谱辐射特性研究

多孔活性金属材料因为内部存在大量的孔隙，大大地增加了与空气的接触面积，使得其在空气中的燃烧较为猛烈，燃烧温度迅速上升。其燃烧过程属于固体燃烧的范畴，较为复杂。以镁为例，通过建立燃烧模型，来研究多孔活性金属的光谱辐射特性。首先，建立氧气总消耗量与活性金属剩余质量的关系，研究氧气在活性金属孔隙内的扩散浓度关系，通过求解活性金属热平衡方程得到活性金属燃烧过程中温度与时间的关系式，进而得到活性金属的峰值光谱辐射强度表达式；然后，将模型计算的仿真结果与红外热像仪测得的实验结果对比，结果表明，模型的计算结果与实验结果相一致，误差在了10%以内；最后，通过建立的燃烧模型来研究活性金属燃烧规律以及其光谱辐射特性，解决了高空、高速下的活性金属光谱辐射强度难以实验获得的问题，大大减小了实验成本与时间。分别对比不同时间活性金属箔片在1～3，3～5以及8～12 μm波段下的辐射强度，得出活性金属燃烧时的辐射强度主要集中在3～5 μm波段的结论。研究结果表明：自燃金属最大燃烧温度随高度的增加逐渐下降，随气流速度的增加先增加后减小，在速度为30 m·s-1时，温度达到最大；自燃金属的光谱辐射强度在2～6 μm波段达到最大。该模型也可以用来研究其他活性金属的燃烧特性。     

聚乙烯吡咯烷酮纳米银荧光增强测定番茄红素

合成了聚乙烯吡咯烷酮纳米银,研究了番茄红素对聚乙烯吡咯烷酮纳米银体系的荧光增强效应。考察了缓冲体系、纳米银用量、聚乙二醇浓度、反应时间和温度等因素的影响,建立了测定番茄红素的新方法。在最佳条件下,体系的相对荧光强度与番茄红素浓度呈良好的线性关系,其线性范围为2.0×10-6~8.0×10-5 mol/L,检出限为1.6×10-8 mol/L。方法应用于实际样品检测,回收率为98.29%~109.36%。     

模板-聚合法Pd/Al2O3催化剂制备及其蒽醌加氢性能研究

以丙烯酸铵为模板剂,由油柱成型法制备了系列球形Al2O3载体,采用XRD、BET等分析测试手段对其晶体结构、比表面积、孔容和孔径分布进行了表征,结果表明,600℃焙烧的球形γ-Al2O3载体具有介孔结构,并且比表面较不使用模板剂的样品有大幅度增加。焙烧温度升至960℃得到δ-Al2O3,介孔结构消失,但由于结构记忆效应,载体的大表面特性得以保持。以δ-Al2O3为载体制备Pd/Al2O3催化剂,采用氢-氧滴定(HOT)方法测定发现,比表面的增加显著提高了Pd金属的分散度,从而大幅度提高了催化剂的蒽醌加氢活性,氢化效率最高可达10.5 g.L-1。     

磷化镍催化剂的制备机理及其加氢脱氮性能

采用热重-质谱联用技术研究了次磷酸盐在氮气中的热分解过程,探讨了次磷酸盐热分解法制备磷化镍的反应机理:次磷酸镍中的Ni²⁺能够"催化"H₂PO₂^-低温发生歧化反应生成PH₃,继而还原Ni²⁺得到Ni₂P。制备了不同负载量的Ni₂P/SiO₂催化剂,用X射线衍射(XRD)、低温N₂吸附-脱附、高分辨透射电镜(HRTEM)等分析技术对催化剂结构进行表征。结果表明,Ni₂P活性组分在SiO₂载体上具有良好的分散性,颗粒粒径为5～8 nm。以喹啉为加氢脱氮模型化合物,在高压微型固定床反应器上对催化剂活性进行评价,在反应温度为360℃、氢气压力为2.0 MPa、液时空速为2.0 h^-1、氢油体积比为500:1时,Ni₂P(20%)/SiO₂催化剂的加氢脱氮率为41.5%。     

Ni-Mo/Al_2O_3催化剂上硫转移反应的研究

制备了以γ-Al2O3为载体的Ni-Mo催化剂,并用于FCC汽油的加氢硫转移反应。对Ni-Mo/Al2O3催化剂上的硫转移反应机理进行了研究,考察了不同反应条件对硫转移反应的影响。实验结果表明,硫醇与烯烃的反应在催化剂表面的加氢活性位上进行,小分子的硫醇发生加氢脱硫,生成吸附态H2S,吸附态的H2S与烯烃反应,生成大分子硫醇和硫醚;另外小分子硫醇还可直接与烯烃发生反应,生成硫醚。提高反应温度、压力、氢油比或降低空速,均可提高催化剂的硫转移反应活性,轻质硫转化率得到明显提高,且单烯选择性还能维持在98%左右。     

Solvent extraction of U(VI) by trioctylphosphine oxide using a room-temperature ionic liquid

The unique physical and chemical properties of room-temperature ionic liquids(RTILs) have recently received increasing attention as solvent alternatives for possible application in the field of nuclear industry, particularly in liquid-liquid separations of radioactive nuclides. We investigated solvent extraction of U(VI) from aqueous solutions into a commonly used ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([C4mim][NTf2]) using trioctylphosphine oxide(TOPO) as an extractant. The effects of contact time, TOPO concentration, acidity, and nitrate ions on the U(VI) extraction are discussed in detail. The extraction mechanism was proposed based on slope analysis and UV-Vis measurement. The results clearly show that TOPO/[C4mim][NTf2] provides a highly efficient extraction of U(VI) from aqueous solution under near-neutral conditions. When the TOPO concentration was 10 mmol/L, the extraction of 1 mmol/L U(VI) was almost complete( 97%). Both the extraction efficiency and distribution coefficient were much larger than in conventional organic solvents such as dichloromethane. Slope analysis confirmed that three TOPO molecules in [C4mim][NTf2] bound with one U(VI) ion and one nitrate ion was also involved in the complexation and formed the final extracted species of [UO2(NO3)(TOPO)3]+. Such a complex suggests that extraction occurs by a cation-exchange mode, which was subsequently evidenced by the fact that the concentration of C4mim+ in the aqueous phase increased linearly with the extraction percent of U(VI) recorded by UV-Vis measurement.     

基于光楔阵列产生光学涡旋阵列的研究

在研究光楔衍射法产生单涡旋的基础上,基于长条形光楔阵列,提出了利用光束阵列衍射产生涡旋阵列的方法.该方法要求光束阵列在平行于光楔边缘方向上的光束间距等于光束直径的整数倍.利用超精密机床采用一体化加工法加工了光楔阵列元件,验证了该方法的可行性.利用空间光调制器快速灵活调整光束阵列的优点,搭建了借助空间光调制器加载达曼光栅衍射产生所需光束阵列的实验光学系统.针对光束阵列与光楔阵列的匹配问题,研究了达曼光栅掩模图基本单元对光束阵列的调控,获得了可调结构的光束阵列.实验产生了拓扑荷一致的光学涡旋阵列,与仿真结果相一致,证明所提方法的有效性.